CN103757222B - The leaching method of pyrolusite - Google Patents
The leaching method of pyrolusite Download PDFInfo
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- CN103757222B CN103757222B CN201310736442.8A CN201310736442A CN103757222B CN 103757222 B CN103757222 B CN 103757222B CN 201310736442 A CN201310736442 A CN 201310736442A CN 103757222 B CN103757222 B CN 103757222B
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- CN
- China
- Prior art keywords
- add
- leaching
- pyrolusite
- sulfuric acid
- nitric acid
- Prior art date
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Manufacture And Refinement Of Metals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The leaching method of the pyrolusite of introduction of the present invention is by≤180 order pyrolusite powders and does not add in the reactor of withstand voltage, resistance to sulfuric acid and nitric acid corrosion containing the high concentrated organic wastewater of phenyl ring material, add the mixing solutions of sulfuric acid and nitric acid, and carry out agitation leach in confined conditions, after leaching for some time, release reactor off-gas, then pass in confined conditions industrial pure oxygen to leaching night be oxidized.
Description
Technical field
The present invention relates to a kind of leaching method of pyrolusite.
Background technology
Pyrolusite is the important source material of producing the materials such as manganese metal, manganous sulfate, Manganse Dioxide, manganous nitrate.Wet processing produces the main technique of above-mentioned materials, leaches operation and be absolutely necessary operation in this technique.In the wet processing producing manganese metal, manganous sulfate, Manganse Dioxide, substantially adopt sulfuric acid leaching system.Due to the MnO in pyrolusite
2be insoluble to sulfuric acid, need MnO by reducing roasting
2be converted into MnO ability sulfuric acid leaching, but the transformation efficiency of roasting only has about 85%, when causing the pyrolusite of sulfuric acid leaching reducing roasting, the leaching yield of metal target manganese is not high, causes the wasting of resources.Although add FeS in Leaching Systems
2can directly leach pyrolusite with sulfuric acid Deng reductive agent, but leaching velocity is slow, extraction temperature is high, and leaching yield is lower.Exploitation leaching yield direct leaching method that is high, the fast pyrolusite of leaching velocity has larger practical value.
Summary of the invention
For the problem that current pyrolusite leaches, the object of the invention is to find the direct leaching method of pyrolusite that a kind of leaching yield is high, leaching velocity is fast, energy consumption is low, it is characterized in that≤180 order pyrolusite powders and do not add in the reactor of withstand voltage, resistance to sulfuric acid and nitric acid corrosion containing the high concentrated organic wastewater of phenyl ring material, add the mixing solutions of sulfuric acid and nitric acid, and carry out agitation leach in confined conditions.Leach after for some time, release reactor off-gas, then pass into industrial pure oxygen in confined conditions leach liquor is oxidized.After oxidation terminates, the slurry of releasing in reactor carries out solid-liquid separation, obtains required infusion solution.Be 1mol/L ~ 4mol/L for the starting point concentration of sulfuric acid in the mixing solutions that leaches, the starting point concentration of nitric acid is 2g/L ~ 10g/L.For the COD in the high concentrated organic wastewater that leaches
crconcentration>=30000mg/L.The add-on of sulfuric acid is 103% ~ 110% of the theoretical amount leached by manganese whole in pyrolusite.The add-on of high concentrated organic wastewater is with per kilogram MnO
2add COD
cr0.185 kilogram ~ 0.200 kilogram calculating adds.The temperature of whole leaching process is 40 DEG C ~ 70 DEG C, and stirring velocity is 50r/min ~ 130r/min.Extraction time is 1h ~ 2h.Pass into O
2oxidization time be 0.5h ~ 1h, relative pressure is 0.1MPa ~ 0.2MPa.
The object of the present invention is achieved like this: airtight and under having high concentrated organic wastewater and nitric acid existent condition, the redox reaction of sulfuric acid leaching pyrolusite can represent with general formula the following:
3(C-H
xO
y)
m+4mHNO
3=4mNO+3mCO
2+zH
2O
3MnO
2+2NO+6H
+=3Mn
2++2HNO
3+2H
2O
Total reaction is:
(C-H
xO
y)
m+2mMnO
2+2mH
+=2mMn
2++mCO
2+zH
2O
Similar Fe
2o
3the total reaction of leaching is:
(C-H
xO
y)
m+2mFe
2O
3+4mH
+=4mFe
2++mCO
2+qH
2O
At oxidation stage, mainly there is Fe
2+oxidizing reaction:
4FeSO
4+O
2+2H
2SO
4=2Fe
2(SO
4)
3+2H
2O
Fe
2(SO
4)
3+3H
2O=Fe
2O
3+3H
2SO
4
Because the organism speed of response in nitric acid and high concentrated organic wastewater is very fast, NO and the MnO of generation
2reaction also very fast, accelerate whole leaching process thus, and realize MnO
2leach more completely.As long as control the add-on of sulfuric acid and high concentrated organic wastewater well, the amount that Fe enters leach liquor just can be reduced.But the add-on of sulfuric acid and high concentrated organic wastewater very little, will affect the leaching yield of leaching velocity and Mn, so the leaching yield in order to ensure Mn, it is inevitable that Fe leaches.Pass through O
2oxidation is by Fe
2+be oxidized to Fe
3+, and then there is hydrolysis reaction, remove portion Fe.The Fe do not eliminated does not need further oxidation follow-up removing in Fe process.
Outstanding advantages of the present invention is: through above-mentioned series reaction, finally makes the Mn in pyrolusite substantially leach completely, improves the leaching yield of Mn, reduces the wasting of resources; Utilize high concentrated organic wastewater to make oxygenant, the improvement not being only high concentrated organic wastewater opens up a new way, and can reduce the leaching cost of pyrolusite, has obvious economic benefit and environmental benefit; Whole leaching process is thermopositive reaction, and temperature of reaction is not high, and energy consumption is low; Because nitric acid is easy to react with the organism in high concentrated organic wastewater, the NO of generation is easy to again and MnO
2reaction, so leaching process speed is fast; Due in leaching process by Fe
2+oxidation is from Fe
3+, the subsequent purification process of leach liquor can be simplified; Process is carried out in confined conditions, avoids the environmental pollution that NO effusion produces.
specific implementation method
Embodiment 1: by 1000g pyrolusite powder (containing manganese 55.5%, Fe
2o
36.7%, particle diameter 180 order) and 3.26L brewing wastewater (containing COD
crsulfuric acid concentration 50000mg/L) prepared with sulfuric acid and nitric acid is 1mol/L, and concentration of nitric acid is that to add volume be in the lining titanium pressure reaction still of 10L to 2g/L mixing solutions 6600ml, and at 40 DEG C ~ 50 DEG C, 2h is leached in airtight stirring (stirring velocity 70r/min).Then O is passed into
2(relative pressure is 0.1MPa) is oxidized 0.5h.According to the assay result of leached mud after cleaning, the leaching yield of manganese is 99.0%.
Embodiment 2: by 10kg pyrolusite powder (containing manganese 55.5%, Fe
2o
36.7%, particle diameter 180 order) and 19.5L Starch Production concentrate waste water (containing COD
crsulfuric acid concentration 90000mg/L) prepared with sulfuric acid and nitric acid is 3mol/L, and concentration of nitric acid is that to add volume be in the lining titanium pressure reaction still of 50L to the mixing solutions 23L of 8g/L, and at 60 DEG C ~ 70 DEG C, 1h is leached in airtight stirring (stirring velocity 60r/min).Then O is passed into
2(relative pressure is 0.15MPa) is oxidized 1h.According to the assay result of leached mud after cleaning, the leaching yield of manganese is 99.6%.
Claims (1)
1.
a kind of leaching method of pyrolusite, it is characterized in that≤180 order pyrolusite powders and do not add withstand voltage containing the high concentrated organic wastewater of phenyl ring material, in the reactor of resistance to sulfuric acid and nitric acid corrosion, add the mixing solutions of sulfuric acid and nitric acid, and carry out agitation leach in confined conditions, after leaching for some time, release reactor off-gas, pass into industrial pure oxygen to be more in confined conditions oxidized leach liquor, after oxidation terminates, the slurry of releasing in reactor carries out solid-liquid separation, obtain required infusion solution, be 1mol/L ~ 4mol/L for the starting point concentration of sulfuric acid in the mixing solutions that leaches, the starting point concentration of nitric acid is 2g/L ~ 10g/L, for the COD in the high concentrated organic wastewater that leaches cr concentration>=30000mg/L, the add-on of sulfuric acid is 103% ~ 110% of the theoretical amount leached by manganese whole in pyrolusite, and the add-on of high concentrated organic wastewater is with per kilogram MnO 2 add COD cr 0.185 kilogram ~ 0.200 kilogram calculating adds, and the temperature of whole leaching process is 40 DEG C ~ 70 DEG C, and stirring velocity is 50r/min ~ 130r/min, and extraction time is 1h ~ 2h, passes into O 2 oxidization time be 0.5h ~ 1h, relative pressure is 0.1MPa ~ 0.2MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310736442.8A CN103757222B (en) | 2013-12-29 | 2013-12-29 | The leaching method of pyrolusite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310736442.8A CN103757222B (en) | 2013-12-29 | 2013-12-29 | The leaching method of pyrolusite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103757222A CN103757222A (en) | 2014-04-30 |
| CN103757222B true CN103757222B (en) | 2016-02-24 |
Family
ID=50524536
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310736442.8A Expired - Fee Related CN103757222B (en) | 2013-12-29 | 2013-12-29 | The leaching method of pyrolusite |
Country Status (1)
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Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB756362A (en) * | 1952-11-26 | 1956-09-05 | Council Scient Ind Res | A method for the utilisation of manganese ore for the production of pure manganese sulphate and the regeneration of the sulphate spent liquid from electrolytic manganese and manganese dioxide baths |
| GB818379A (en) * | 1954-10-12 | 1959-08-19 | Electrolytic Metal Corp Propri | Treatment of manganese solutions |
| CN100451139C (en) * | 2006-09-21 | 2009-01-14 | 广西大学 | Gray manganese ore leaching out process |
| CN101845562B (en) * | 2010-06-22 | 2013-03-20 | 陈榜龙 | Improved device and method for producing electrolytic manganese metal by two-ore method |
| CN101886168B (en) * | 2010-07-14 | 2012-05-30 | 广西大学 | Extraction technology of semi-manganese oxide ore |
| CN102676807B (en) * | 2012-05-18 | 2014-03-26 | 中南大学 | Method for leaching manganese oxide |
| CN103422118B (en) * | 2013-07-18 | 2016-07-06 | 成都易态科技有限公司 | The electrolytic manganese metal that the method for method for producing electrolytic manganese metal by two-ore and two-control region produce |
-
2013
- 2013-12-29 CN CN201310736442.8A patent/CN103757222B/en not_active Expired - Fee Related
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